Synthesis of bis(indolyl) methanes using aluminiumoxide(acidic) in dry media

Heterogeneous catalyst aluminium oxide(acidic) is found to be an effective catalyst for the solvent-free condensation reaction of indole with aldehydes in microwave irradiation with shorter reaction time and higher yields.

Efficient synthesis of bis(indolyl) methanes catalyzed by(PhCH_2PPh_3)^+Br_3^- under solvent-free conditions

Benzyltriphenylphosphonium tribromide（BTPTB） has been applied as an efficient catalyst for the preparation of bis（indolyl）-methanes （BIMs） via electrophilic substitution of indoles with aldehydes in the absence of solvent.

Oxalic acid as a catalyst for efficient synthesis of bis-(indolyl)methanes,and 14-aryl-14H-dibenzo[a,j]xanthenes in water

A simple, efficient, and environment benign route was developed for the preparation of bis-（indolyl）methanes and 14-aryl-14H- dibenzo[aj]xanthenes from condensation of various aromatic aldehydes or ketones with indole, and 2-naphthol, respectively, using oxalic acid catalyst in aqueous medium. Use of cheap and easily available catalyst, better yields and simple reaction protocol are the advantages of the present method.

n-Dodecylbenzene Sulfonic Acid (DBSA) as a Novel Brønsted Acid Catalyst for the Synthesis of Bis(indolyl)methanes and Bis(4-hydroxycoumarin-3-yl)methanes in Water

n-Dodecylbenzene sulfonic acid (DBSA) as a novel, biodegradable, and efficient Br?nsted acid catalyst used for the reaction of indoles/4-hydroxy coumarin with aldehydes to obtain a bis(indolyl)methanes/bis(4-hydroxycoumarin-3-yl)methanes, respectively. The catalyst exhibited remarkable activity, and tolerated a wide variety of functional groups providing the desired bis(indolyl)methanes and bis(4-hydroxycoumarin-3-yl)methanes in good to excellent yield (70%-96%) in water.

Efficient and Eco-friendly Process for the Synthesis of Bi(indolyl)methanes Catalyzed by Sodium Hydrogensulfate Monohydrate in Ionic Liquid n-Butylpyridinium Tetrafluoroborate

Efficient electrophilic substitution reaction of indoles with various aromatic aldehydes were carried out with a catalytic amount of sodium hydrogensulfate monohydrate （NaHSO4·H20） in ionic liquid n-butylpyridinium tetrafluoroborate （[Bpy]BF4） to afford the corresponding bi（indolyl）methanes in excellent yields. The notable advantages of this protocol in terms of low cost of catalyst and ionic liquid, mild conditions, simple operation, short reaction time, high yields and recycling of the ionic liquid.

SbCl_3 Catalyzed Solventless Synthesis of Bis(indolyl)alkanes under Grinding

A clean and efficient method for the synthesis of bis（indolyl）alkanes with antimony trichloride（SbCl3） as the catalyst under solvent-free grinding conditions is described. This method provides several advantages, such as simple work-up procedure, neutral conditions and high yields.

New Green Synthesis and Antineoplastic Activity of Bis (3-Arylimidazolidinyl-1) Methanes

A new green synthesis and anti-tumor activity of the series of bis (3-arylimidazolidinyl-1) methanes 1 - 6 are described. The compounds were synthesized from the corresponding N-arylethylenediamine and trioxane as sources of formaldehyde and the reactions were performed in heterogeneous phase catalyzed by an acidic ion-exchange resin (Amberlyst 15). The compounds were tested with the Sulforhodamine B assay according to the protocol of the National Cancer Institute for several cell lines. The results were expressed as percentage inhibition of growth cell in comparison with the full growth of the cells without treatment. Cytotoxicity on normal cells using the Annexing-PI staining and flow cytometry has been evaluated. The parent compound, bis(3-phenylimidazolidinyl-1)methane 1 and the monohalogenated derivatives 4-chlorophenyl 3 and 3-bromophenyl 5 showed antineoplastic activity, 60%, 82% and 89% inhibition growth cell respectively on the human colon cell line (HCT116). The 4-tolyl derivative 6 presented inhibitory activity (73% inhibition of growth cell) on human lung adenocarcinoma cell line (A549) and 62% on human mammary cell line MCF-7.

THE CONDENSATION REACTION OF BIS(PERFLUOROALKANESULFONYL)METHANES WITH AROMATIC ALDEHYDES

The ccndensation reactions occurred when heating bis(perfluoroalkane- sulfonyl)methanes with aromatic aldehydes in acetic acid anhydride and gave high yields of 1-aryl-2,2-di(perfluoroalkanesulfonyl)ethylenes The perfluoroalkanesulfonyl groups R_FSO_2 are known as the strongest electron-attracting substituents^(1-2).This property is often used in the activation of C-C multiple and 2,2'-C-H bonds.The synthesis and reactions of perfluoroalkanesulfonyl substituted alkenes and alkynes are of great interest in synthetic organic chemistry^(3-6). Recently,Hanack^7 reported the preparation of 2-aryl-l-(perfluoroalkane- sulfonyl)acrylonitrile R_FSO_2C(CN)=CHAr.However,he failed to obtain the 1,1-di(perfluoroalkanesulfonyl)alkenes by the Knoevenagel reaction of bis(perfluoroalkanesulfonyl)methane with aldehydes.

甲烷裂解双分散孔催化剂颗粒积碳行为模拟

【目的】为了更好地理解催化剂颗粒的积碳行为,分析积碳效应下催化剂颗粒界面反应传质特性,实现对催化剂颗粒的优化设计与调控。【方法】采用颗粒解析模型,考虑积碳引起的孔隙结构动态演变以及反应性能的衰减,分别探讨单分散孔和双分散孔颗粒积碳形成及所引起的孔隙结构演变规律。【结果】积碳失活从多孔颗粒表层向内部核心移动,扩散主导机制转向反应主导机制;相较于单分散孔颗粒,双分散孔颗粒具备更强的抗积碳性能;固定床反应器中催化剂颗粒分布影响积碳行为,壁面处积碳更加严重,更容易导致失活。【结论】选择双分散孔催化剂颗粒对于积碳行为具有改善作用,同时应选择合适的长径比反应器,削弱壁面效应对积碳行为的影响。

Heterotetranuclear Cu_2~IPd_2~Ⅱ Complex with Bis(diphenylphosphino)methane and Diethyldithiocarbamate

Self-assembly between the building blocks of Pd(Et2dtc)2 (Et2dtc = diethyldithio- carbamate) and [Cu2(m-dppm)2(MeCN)2]2+ (dppm = bis(diphenylphosphino)methane) gave a new heterotetranuclear complex [Cu2Pd2(m-dppm)2(m-Et2dtc)2(m3-Et2dtc)2](ClO4)2H2O (C70H86Cl2Cu2- N4O9P4Pd2S8, Mr = 1932.56), and its crystal structure has been determined by X-ray crystallo- graphy. It crystallizes in triclinic, space group P with a = 11.9834(6), b = 12.5624(6), c = 14.5603(8) ? a = 101.393 (1), b = 103.300 (1), g = 96.310(1), V = 2063.2(2) 3, Z = 1, Dc = 1.544 g/cm3, m(MoKa) = 1336 cm-1 and F(000) = 978. The total and unique reflections are 8710 and 5400, respectively. The structure was refined to R = 0.0860 and wR = 0.1996 for 3914 observed reflections with I > 2s(I). The title complex consists of the cation [Cu2Pd2(m-dppm)2(m-Et2dtc)2(m3- Et2dtc)2]2+, anion ClO4- and solvate H2O. The Pd(Ⅱ) atoms are located at the approximately square-planar environments with PS3 donors and the Cu(I) atoms display distorted tetrahedral geometries.

A New Ternary Fluorescent Europium Complex with Bis(Diphenyl Phosphine Oxide) Methane and Thenoyltrifluoroacetone

A fluorescent ternary europium complex containing bis (diphenyl phosphine oxide) methane which functioned as both a neutral and anion ligand, and thenoyltrifluoroacetonato anion was synthesized and characterized by elemental analysis, DTA TG analysis, UV Vis, FT IR and MS spectroscopy. The chemical formula is proved to be Eu(TTA)(MPPO)(HMPPO)·(NO 3)·2H 2O. Its luminescence quantum efficiency(in acetonitrile, 26 3%) is approximately the same as that of the commonly used red emission luminescent compound, Eu(TTA) 3(TPPO) 2 (TPPO is triphenyl phosphine oxide). The new complex has comparatively long fluorescence lifetime.

Construction of a New Two-fold Interpenetrated Three-dimensional Cobalt(Ⅱ)Coordination Polymer Based on 2,5-Thiophenedicarboxylic Acid and Bis(imidazol-1-yl)methane

A cobalt coordination polymer, {[Co2（tdc）2（bimm）2]·（3 DMF）}n, was synthesized based on 2,5-thiophenedicarboxylic acid（H2 tdc） and bis（imidazol-1-yl）methane（bimm） mixed ligands. The asymmetric unit of the complex contains two Co2＋） cations, two tdc2-dianions, two neutral bimm ligands, and three free DMF molecules. In the complex, deprotonated tdc2-dianions alternately bridge the adjacent Co2＋ cations to generate chains, which are further connected by the flexible bimm ligands to form a 3 D structure containing adamantanoid-like subunits. In topology, the structure of 1 represents a 4-connected uninodal two-fold interpenetrated dia（66） topology. Moreover, the solid UV-Vis absorption spectra of the complex have also been investigated.

Total synthesis of bis-(2,3-dibromo-4,5-dihydroxyphenyl)-methane as potent PTP1B inhibitor

Protein tyrosine phosphatase 1B （PTP1B） plays an important role as a negative regulator and has been proved to be an effective target for the treatment of type 2 diabetes mellitus. Bis-（2,3-dibromo-4,5-dihydroxyphenyl）-methane 7 was first reported as a natural bromophenol with significant inhibition against PTP1B which was isolated from red algae Rhodomela conrervoides. Intrigued by its astonishing activity （IC50 = 2.4 μmol/L）, compound 7 was synthesized with the overall yield of 24% and evaluated for its PTPIB inhibitory activity compared with natural compound.

Synthesis and Crystal Structure of Bis(μ-bis(diphenyl- phosphino)methane)(μ-benzenethiolate)(acetonitrile) Dicopper(I) Perchlorate Diethylether Solvate

The reaction between [Cu2(m-dppm)2(MeCN)4](ClO4)2(dppm = bis(diphenylphos- phino)methane) and [Zn(PhS)2(bpy)] (bpy = 2,2-bipyridine, PhS = benzenethiolate) gave the complex [Cu2(m-dppm)2(m-PhS)(MeCN)]ClO40.5(Et2O)(C58H52ClNO4P4SCu20.5Et2O) which was determined by X-ray single-crystal diffraction. The crystal is of orthorhombic, space group P212121 with a = 13.6157(3), b = 20.8022(6), c = 21.3299(6) ? V = 6041.4(3) 3, Mr = 1182.54, Dc = 1.300 g/cm3, F(000) = 2444, m = 0.934 mm-1 and Z = 4. The final R = 0.0773 and wR = 0.1843 for 7744 observed reflections (I > 2s(I)). The dicopper atoms are doubly bridged by dppm as well as one S donor from benzenethiolate. One copper atom is in a distorted trigonal bipyramidal environ- ment, whereas the other adopts a distorted tetrahedral geometry.

Syntheses and Crystal Structures of Two Heterobimetallic Clusters [WOS_3Cu_3I(dmpzm)_2]·2(MeCN)_(0.5) and [WS_4Cu_4I_2(dmpzm)_2]·DMF(dmpzm=Bis(3,5-dimethylpyrazolyl)methane)

The reaction of [Et4N]2WOS3 with three equiv.of CuI and dmpzm in MeCN afforded [WOS3Cu3I（dmpzm）2]·2（MeCN）0.5（1·2（MeCN）0.5） while that of [PPh4]2WS4 with four equiv.of CuI in DMF/MeCN followed by the addition of two equiv.of dmpzm in MeOH gave rise to [WS4Cu4I2（dmpzm）2]·DMF（2·DMF）.Both compounds were characterized by elemental analysis,IR,and single-crystal X-ray diffraction analysis.1·2（MeCN）0.5 crystallizes in triclinic,space group P1-with a = 11.4552（5）,b = 11.6735（3）,c = 16.2278（9） ,α = 99.537（9）,β = 101.986（2）,γ = 118.464（13）o,V = 1775.5（3）3,Z = 2,μ = 6.080 mm-1,Dc = 1.983 Mg/m3,T = 193（2） K,C24H35Cu3IN9OS3W,Mr = 1063.22,F（000） = 1018,S = 1.060,R = 0.0376 and wR = 0.0870.2·DMF belongs to the orthorhombic system,space group Pmn21 with a = 22.145（4）,b = 11.464（2）,c = 7.7370（15） ,V = 1964.2（6）3,Z = 2,μ = 6.865 mm-1,Dc = 2.189 Mg/m3,T = 193（2） K,C25H39Cu4I2N9OS4W,Mr = 1301.72,F（000） = 1226,R = 0.0632,wR = 0.1706 and S = 1.130.1·2（MeCN）0.5 consists of one CuI and two [Cu（dmpzm）]＋ fragments that are linked by [WOS3]2-species via six Cu-S bonds,forming a nido-like [WS3Cu3] core.2·DMF contains a saddle-shaped [WS4Cu4] core with two iodides coordinated at two Cu centers in a cis position and two dmpzm ligands being chelated at another two Cu centers in a cis position.

Synthesis and Crystal Structure of [Ni(bdpm)_2(OAc)]_2(N_3)_2·5H_2O(bdpm=Bis(3,5-dimethylpyrazol-1-yl)methane,OAc=CH_3COO^-)

A Ni（Ⅱ） complex [Ni（bdpm）2（OAc）]2（N3）2.5H20 （bdpm = bis（3,5-dimethylpyrazol-1-yl）-methane） was synthesized and characterized by elemental analysis, 1R and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a = 18.630（2）, b = 16.6624（19）, c = 19.821（2） A, fl = 90.146（2）°, V = 6152.9（12） A3, Z = 4, C48H80N22Ni2O9, Mr = 1226.76, Dc = 1.324 g/cm^3, F（000） = 2600 and μ = 0.680 mm^-1. The structure was refined to the final R = 0.0578 and wR = 0.1337 for 10848 independent reflections （Rint = 0.0311） and 6915 observed reflections （1 〉 2σ（I））. The complex contains two asymmetric molecules in the cell with small difference in bond distances and bond angles. Each Ni（Ⅱ） ion is bound by four nitrogen atoms of two chelating bdpm groups in a six-membered boat conformation and two oxygen atoms from one chelating bidentate acetate group to form a distorted octahedral geometry. The complex also contains azide anion outside acting as counteranion and two crystalline water molecules to link two discrete mononuclear cations though hydrogen bonds.

A practical synthesis of bis(indolyl)methanes catalyzed by BF_3·Et_2O

Practical BF3.Et20 catalyzed reactions between indoles and a series of carbonyl compounds at room temperature are described, which afford bis（indolyl）methanes with isolated yields up to 96%,

Synthesis of bis(indolyl) methanes catalyzed by Schiff base-Cu(Ⅱ) complex

Schiff base-Cu（II） complex is found to be an effective catalyst for the condensation reaction of indole with aldehydes using ethanol as the solvent. The characterization of the catalysts was carried out using XRD and FT-IR.

Surfactant-assisted synthesis of bis(indolyl)methanes in water

An environmentally friendly synthesis method for bis（indolyl）methanes has been developed in the presence of sodium lauryl ether sulfate（SLES）,electrophilic substitution reactions of indoles with aldehydes were accomplished in water as solvent at room temperature without any Bronested or Lewis acid catalysts.

Highly Efficient Synthesis of Bis（indolyl）methanes Catalyzed by Sodium Tetrafluoroborate

Sodium tetrafluoroborate （NaBF4） was found to catalyze the electrophilic substitution reactions of indoles with aldehydes and ketones under solvent-free conditions to afford the corresponding bis（indolyl）methanes in high yields.